CN111097389B

CN111097389B - Continuous production system and method for crosslinked maleic acid ionomer microspheres

Info

Publication number: CN111097389B
Application number: CN201811252500.9A
Authority: CN
Inventors: 宋文波; 袁浩; 胡慧杰; 刘振杰; 张晓萌
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2018-10-25
Filing date: 2018-10-25
Publication date: 2022-03-15
Anticipated expiration: 2038-10-25
Also published as: CN111097389A

Abstract

The invention relates to the field of continuous production of crosslinked maleic acid ionomer microspheres, and discloses a system and a method for preparing crosslinked maleic acid ionomer microspheres. The system comprises: a copolymerization unit, a reaction unit for generating ionomer, a washing unit, a drying unit and a solvent recovery unit which are communicated in sequence; the comonomer is subjected to copolymerization unit and first separation to obtain a separated solid-containing phase and a separation liquid-I; separating the solid phase, reacting in a reaction unit for generating ionomer, and performing second separation to obtain a centrifugal slag phase, a water phase and a separation liquid-II; the washing unit is used for carrying out alcohol washing and third separation on the centrifugal slag phase to obtain an ionomer slag phase and a washing clear liquid; drying the ionomer slag phase to obtain cross-linked maleic acid ionomer microspheres; removing impurities from the separation liquid-I, the separation liquid-II and the washing clear liquid through a solvent recovery unit to obtain products, and returning the products to the copolymerization unit and the washing unit respectively; the system is used for realizing continuous production of the crosslinked maleic acid ionomer microspheres. Can realize continuous preparation of the ionomer.

Description

Continuous production system and method for crosslinked maleic acid ionomer microspheres

Technical Field

The invention relates to the field of continuous production of crosslinked maleic acid ionomer microspheres, in particular to a continuous production system and a continuous production method of crosslinked maleic acid ionomer microspheres.

Background

The ionic polymer is ionomer or ionomer, and is a polymer material with a small amount of ionic groups on a high molecular chain, wherein the molar content of the ionic groups is not more than 15%. The ionomer is a perfect combination of inorganic ions and organic molecules, and due to the introduction of ionic groups, the molecules in the ionomer have special interaction which is not existed in general polymers, such as ion-ion interaction; ion pairs interact with ion pairs; the ion interacts with the dipole; hydrogen bonding interactions, and the like. These specific interactions give ionomers many unique properties and have important applications in polymer modification, functional materials, etc.

In addition, the research on the preparation and application of the polymer microspheres is a hotspot in the field of functional polymer materials, and the polymer microspheres from nano-scale to micron-scale have the special properties of large specific surface area, strong adsorbability, large coacervation effect and strong surface reaction capability, and can be widely applied to many high and new technical fields.

Yan philosophy, Qiang xi Huai, etc. in the text of "preparation of fatty alcohol monoester sodium salt of styrene/maleic anhydride copolymer and surface activity thereof" ((daily chemical industry, 2012, 42 (2): 97-100)), 1, 4-dioxane is used as solvent, p-toluenesulfonic acid is used as catalyst, and higher fatty alcohol monoester sodium salt of styrene/maleic anhydride copolymer is prepared.

According to the research on the synthesis and pH sensitivity of SMA ethylation products in the fields of Louisteine and Sunweian, etc. (applied chemical engineering, 2008, 37 (5): 498-501) ethyl ketone is used as a solvent and triethylamine is used as a catalyst to prepare the ethyl ester of the styrene/maleic anhydride copolymer, and the reaction mixture is precipitated in petroleum ether, filtered, dried, dissolved again in tetrahydrofuran, precipitated in petroleum ether again, filtered and dried to obtain the product.

At present, no matter polymer microspheres or ionomer microspheres, the industrial production must face the washing purification and solid-liquid separation of ultrafine particles, and the current common method is a three-leg centrifuge or a plate-frame filter, so that the sudden idle operation exists, and the process continuity and safety need to be improved.

Disclosure of Invention

The invention aims to overcome the problems of difficult washing purification and solid-liquid separation of ultrafine particles in industrial production of crosslinked maleic acid ionomer microspheres, and provides a system and a method for preparing the crosslinked maleic acid ionomer microspheres.

In order to achieve the above object, a first aspect of the present invention provides a system for preparing crosslinked maleic acid ionomer microspheres, the system comprising:

a copolymerization unit, an ionomer-producing reaction unit, a washing unit, a drying unit, and a solvent recovery unit, which are connected in series, wherein,

the copolymerization unit is used for carrying out copolymerization reaction on a comonomer, and the obtained polymer mother liquor containing the maleic anhydride-based copolymer microspheres is continuously subjected to first separation to obtain a separated solid-containing phase and a separation liquid-I;

the reaction unit for generating the ionomer is used for reacting the separated solid-containing phase and continuously carrying out second separation on the prepared product to obtain a centrifugal slag phase containing ionomer microspheres, a water phase and a separation liquid-II;

the washing unit is used for carrying out at least one time of alcohol washing and continuous third separation on the centrifugal slag phase to obtain an ionomer slag phase and a washing clear liquid;

the drying unit is used for drying the ionomer slag phase to obtain the crosslinked maleic acid ionomer microspheres;

the solvent recovery unit is used for removing impurities from the separation liquid-I, the separation liquid-II and the washing clear liquid, and returning the recovered solvent and the recovered alcohol obtained by separation to the copolymerization unit and the washing unit respectively;

the system is used for realizing continuous production of the crosslinked maleic acid ionomer microspheres.

In a second aspect, the present invention provides a method for preparing crosslinked maleic acid ionomer microspheres using the system of the present invention, comprising:

(1) carrying out copolymerization reaction on maleic anhydride, a monomer B shown in a formula (I), an initiator, a cross-linking agent and a reaction solvent in a copolymerization unit of a system to obtain a polymer mother liquor containing maleic anhydride-based copolymer microspheres;

(2) carrying out continuous first separation on the polymer mother liquor to obtain a separated solid-containing phase and a separation liquid-I;

(3) reacting the separated solid-containing phase with alkali liquor, and continuously carrying out second separation on the obtained product to obtain a centrifugal slag phase containing ionomer microspheres, a water phase and a separation liquid-II;

(4) introducing the centrifugal slag phase into a washing unit of a system, and performing at least one alcohol washing and third separation to obtain an ionomer slag phase and a washing clear liquid;

(5) sending the ionomer slag phase into a drying unit of a system for drying to obtain cross-linked maleic acid ionomer microspheres;

(6) introducing the separation liquid-I, the separation liquid-II and the washing clear liquid into a solvent recovery unit of a system, and respectively returning the recovered solvent and the recovered alcohol obtained by recovery to the steps (1) and (4);

r is H or methyl.

Through the technical scheme, the invention provides a system and a method for continuously preparing the maleic acid ionomer with the cross-linking and microsphere structures. The technological process of the method can realize continuous solid-liquid centrifugal separation of the superfine copolymerization product or the ionomer microsphere and the solvent, and the used reaction solvent and the washed alcohol solvent can be recycled. The method provided by the invention can save the separation process which is manually operated among the units of the system in the prior art, effectively avoid the sudden empty operation of the solvent, realize the continuous reaction, washing and separation processes for preparing the ionomer microspheres, effectively stabilize the separation effect and avoid the frequent start-up and shutdown operations of the centrifuge. The average particle size of the obtained microspheres can be 600-2000 nm.

Drawings

FIG. 1 is a graph of the infrared spectrum of the maleic acid ionomer microsphere obtained in example 1;

FIG. 2 is a scanning electron micrograph of the maleic acid ionomer microsphere obtained in example 1;

FIG. 3 is a first schematic diagram of a system for preparing maleic acid ionomer microspheres according to the present invention;

FIG. 4 is a second schematic diagram of a system for preparing maleic acid ionomer microspheres according to the present invention;

fig. 5 is a schematic flow chart of a method for preparing maleic acid ionomer microspheres according to the present invention.

Description of the reference numerals

V-13 reaction solvent storage tank R-11 reaction liquid mixing kettle R-12 copolymerization reactor

S-21 first disk centrifuge A-21 first on-line turbidimeter V-25 separated liquid storage tank

R-21 alkali dissolving kettle R-22 ionomer reactor V-21 alkali liquid kettle

A-22a second on-line turbidimeter A-22b third on-line turbidimeter S-22 second disk centrifuge

R-32 washing kettle V-36 clear liquid storage tank V-37 alcohol storage tank

S-31 third disc centrifuge A-31 fourth on-line turbidimeter G-41 drier

E-41 condenser V-41 drying condensate tank T-51 alcohol rectifying tower

E-51 alcohol heat exchanger E-52 raffinate reboiler V-51 alcohol condensate tank

T-52 reaction solvent rectifying column E-53 solvent heat exchanger E-54 waste liquid reboiler

V-53 solvent condensate tank V-55 feed tank

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In a first aspect, the present invention provides a system for preparing crosslinked maleic acid ionomer microspheres, as shown in fig. 3, comprising:

According to the present invention, preferably, the copolymerization unit includes: a reaction solvent storage tank V-13, a reaction liquid mixing kettle R-11, a copolymerization reactor R-12, a first disk centrifuge S-21, a first online turbidity meter A-21 and a separation liquid storage tank V-25; wherein the reaction solvent storage tank V-13 is used for storing a reaction solvent; the reaction liquid mixing kettle R-11 is used for mixing the reaction solvent and a plurality of reaction raw materials into reaction liquid; the copolymerization reactor R-12 is used for continuously carrying out the copolymerization reaction on the reaction liquid; and continuously flowing the obtained polymer mother liquor into a first disc centrifuge S-21 for continuous first separation, and introducing the obtained separation liquid into a copolymerization reactor R-12 or a separation liquid storage tank V-25 after passing through a first online turbidity meter A-21.

In the invention, the copolymerization reactor can be selected from a tubular reactor, a groove type baffled reactor or two full mixing kettle type reactors connected in parallel.

According to the invention, a first online turbidimeter A-21 is used to monitor the turbidity of the separated liquid-I separated by the first disk centrifuge S-21, in order to control the flow direction of the separated liquid-I. Preferably, valves are respectively arranged between the first on-line turbidity meter A-21 and the copolymerization reactor R-12 and between the first on-line turbidity meter A-21 and the separation liquid storage tank V-25, and are used for introducing the separation liquid-I into the separation liquid storage tank V-25 when the turbidity of the separation liquid-I reaches the standard and introducing the separation liquid-I into the copolymerization reactor R-12 when the turbidity of the separation liquid-I does not reach the standard. By "reached" is meant that the turbidity of the separation medium-I is lower than a predetermined value, for example 0.1% by weight (turbidity value corresponding to a turbid solution of 0.1g of polymeric microspheres dispersed in 100g of solvent).

In the context of the present invention, turbidity is the degree of turbidity of a mixture which appears macroscopically in the homogeneously mixed mixture as a result of absorption, scattering or refraction of light by suspended particles, the value of which is determined using a turbidimeter. The turbidity value is related to the nature and concentration of the particles, and thus can be used as an indicator of the concentration of particles for the same type of particles, and is characterized here by the concentration of particles (mass in g of particles in 100g of solvent, in% by weight).

In the present invention, a water separating bag disposed at the lower part of the reaction solvent storage tank V-13 may be used for removing a small amount of water contained in the recovered solvent.

In the system provided by the invention, the high-concentration reaction liquid discharged from the copolymerization reactor R-12 can avoid the separation process of manual operation in the prior art, and the first disk centrifuge S-21 and the first online turbidity meter A-21 which are arranged between the copolymerization reactor R-12 and the ionomer reactor R-22 are used in a matching way, so that the continuous first separation of the reaction liquid can be realized, the exposure of the reaction liquid is reduced, and the explosion operation is avoided.

In this context, the high concentration is relative to: the existing disk centrifuge is generally applied to the separation of low-concentration turbid liquid with solid content less than 5 weight percent.

According to the invention, the ionomer-generating reaction unit comprises: an alkali dissolving kettle R-21, an alkali liquor tank V-21, an ionomer reactor R-22, a second disc centrifuge S-22, a second online turbidimeter A-22a and a third online turbidimeter A-22 b; wherein, the alkali dissolving kettle R-21 is used for dissolving alkali in water to be alkali liquor; a lye tank V-21 for storing the lye therefrom to provide the reaction; an ionomer reactor R-22 for said reacting said separated solid-containing phase with said caustic; and continuously flowing the obtained ionomer reaction solution into a second disc centrifuge S-22 for continuous second separation, and introducing the obtained water phase into an ionomer reactor R-22, a separation solution storage tank V-25 or an alkali dissolution kettle R-21 after passing through a second online turbidimeter A-22a and a separation solution-II through a third online turbidimeter A-22 b.

In the present invention, the ionomer reactor may be selected from a shell and tube reactor, a tank baffled reactor or a full mixing tank reactor

According to the invention, valves are respectively arranged between a second online turbidimeter A-22a and an ionomer reactor R-22, between the second online turbidimeter A-22a and an alkali dissolution kettle R-21, between a third online turbidimeter A-22b and the ionomer reactor R-22, and between the third online turbidimeter A-22b and a separating liquid storage tank V-25, and are used for introducing the separating liquid-II into the separating liquid storage tank V-25 when the turbidity of the separating liquid-II reaches the standard, introducing the aqueous phase into the alkali dissolution kettle R-21 when the turbidity of the aqueous phase reaches the standard, and introducing the aqueous phase and the separating liquid-II into the ionomer reactor R-22 when the turbidity of the aqueous phase does not reach the standard. By achievement of a standard is meant that the turbidity of the separated liquid-II is below a preset value, such as 0.1% by weight.

In the invention, the high-concentration ionomer reaction liquid discharged from the ionomer reactor R-32 can avoid the separation process of manual operation in the prior art, and the second disc centrifuge S-22, the second online turbidimeter A-22a and the third online turbidimeter A-22b which are arranged between the ionomer reactor R-22 and the washing kettle R-32 are used in a matching way, so that the second separation of the ionomer reaction liquid can be continuously carried out, the exposure of the ionomer reaction liquid is reduced, and the open operation is avoided.

According to the invention, the washing unit comprises: an alcohol storage tank V-37, a clear liquid storage tank V-36 and at least one set of washing devices, each set of washing devices comprising: a washing kettle R-32, a third disc centrifuge S-31 and a fourth online turbidimeter A-31; wherein the alcohol storage tank V-37 is used for storing alcohol solvent; the washing kettle R-32 is used for continuously carrying out alcohol washing on the centrifugal slag phase and the alcohol solvent to obtain dispersed slurry; and continuously introducing the dispersed slurry into a third disc centrifuge S-31 for continuous third separation, and introducing the obtained washing clear liquid into a washing kettle R-32 or a clear liquid storage tank V-36 after passing through a fourth online turbidity meter A-31.

According to the invention, valves are respectively arranged between the fourth online turbidity meter A-31 and the washing kettle R-32, and between the fourth online turbidity meter A-31 and the clear liquid storage tank V-36, and are used for introducing the washing clear liquid into the clear liquid storage tank V-26 when the turbidity of the washing clear liquid reaches the standard, and introducing the washing clear liquid into the washing kettle R-22 when the turbidity does not reach the standard.

In the present invention, the washing unit may include a plurality of groups of the washing devices, for example, the centrifugal residue phase separated by the third disk centrifuge S-31 in the previous group is continuously fed into the next group of the washing devices, alcohol washing is performed with the alcohol solvent, the same continuous third separation as above is performed, and finally the residue phase satisfying the alcohol washing effect enters the drying unit of the system provided by the present invention.

In the invention, the high-concentration dispersed slurry discharged from the washing kettle R-32 can avoid the separation process of manual operation in the prior art, and the continuous third separation of the dispersed slurry can be realized by using the cooperation of the third disc centrifuge S-31 and the fourth online turbidity meter A-31 arranged between the washing kettle R-32 and the dryer G-41, so that the exposure of the dispersed slurry is reduced, and the sudden emptying operation is avoided.

According to the invention, the drying unit comprises: a dryer G-41, a condenser E-41 and a drying condensate tank V-41; the dryer G-41 is used for drying the ionomer slag phase to obtain the crosslinked maleic acid ionomer microspheres; the condenser E-41 is communicated with the drying condensate tank V-41 and is used for condensing the gaseous solvent discharged by the condensing dryer G-41 into liquid and introducing the liquid into the drying condensate tank V-41; the drying condensate tank V-41 is communicated with an alcohol storage tank V-37.

In the present invention, the dryer G-41 may be, for example, a microwave dryer, a microwave vacuum dryer, or a rake vacuum dryer.

To facilitate drying, the drying gel tank V-41 may also be connected to a vacuum device.

According to the present invention, as shown in fig. 4, the solvent recovery unit includes: an alcohol solvent recovery device and a reaction solvent recovery device; the alcohol solvent recovery device is communicated with the clear liquid storage tank V-36, the alcohol storage tank V-37 and the reaction solvent recovery device, and is used for recovering the alcohol solvent in the washing clear liquid from the clear liquid storage tank V-36, returning the alcohol solvent to the alcohol storage tank V-37, and simultaneously introducing residual liquid of the washing clear liquid into the reaction solvent recovery device; and the reaction solvent recovery device is communicated with the separation liquid storage tank V-25 and the reaction solvent storage tank V-13, is used for recovering the separation liquid from the separation liquid storage tank V-25 and the reaction solvent in the residual liquid, and returns to the reaction solvent storage tank V-13. The separation liquid in the separation liquid tank V-25 may include a separation liquid-I from the copolymerization unit, and a separation liquid-II from the ionomerization unit.

According to the present invention, the alcohol solvent recovery apparatus comprises: an alcohol rectifying tower T-51, an alcohol heat exchanger E-51, an alcohol condensate tank V-51 and a raffinate reboiler E-52; wherein the alcohol rectifying tower T-51 is used for distilling clear liquid from the clear liquid storage tank V-36, and alcohol vapor discharged from the top of the alcohol rectifying tower T-51 sequentially passes through the alcohol heat exchanger E-51 and the alcohol condensate tank V-51 to obtain recovered alcohol; one part of the recovered alcohol is returned to the alcohol rectifying tower T-51, and the other part of the recovered alcohol is returned to the alcohol storage tank V-37 to be reused in the washing unit; and discharging raffinate from the bottom of the alcohol rectifying tower T-51, wherein one part of the raffinate passes through a raffinate reboiler E-52 and then returns to the alcohol rectifying tower T-51, and the other part of the raffinate is introduced into the reaction solvent recovery device.

In the present invention, the alcohol rectification column T-51 may be a normal pressure or micro positive pressure column for refining the alcohol in the clear liquid. A metering pump can be arranged between the alcohol condensate tank V-51 and the alcohol rectifying tower T-51.

According to the present invention, the reaction solvent recovery apparatus comprises: a feeding tank V-55, a reaction solvent rectifying tower T-52, a solvent heat exchanger E-53, a solvent condensate tank V-53 and a waste liquid reboiler E-54; wherein the feed tank V-55 is communicated with the bottom of the alcohol rectifying tower T-51 and the separated liquid storage tank V-25 and is used for mixing the residual liquid and the separated liquid from the separated liquid storage tank V-25 to be used as feed; the reaction solvent rectifying tower T-52 is used for fractionating the feed, and the solvent vapor discharged from the top of the reaction solvent rectifying tower T-52 passes through the solvent heat exchanger E-53 and the solvent condensate tank V-53 in sequence to obtain a recovered solvent; one part of the recovered solvent is returned to the reaction solvent rectifying tower T-52, and the other part of the recovered solvent is returned to the reaction solvent storage tank V-13 to be reused in the copolymerization unit; and discharging waste liquid from the bottom of the reaction solvent rectifying tower T-52, wherein one part of the waste liquid returns to the reaction solvent rectifying tower T-52 after passing through a waste liquid reboiler E-54, and the other part of the waste liquid is discharged.

In the present invention, the reaction solvent rectification column T-52 is used to refine the reaction solvent in the feed from the feed tank V-55. A metering pump can be arranged between the solvent condensate tank V-53 and the reaction solvent rectifying tower T-52.

In the invention, the reaction solvent recovery device can also be provided with a communicated vacuum system, which can promote the efficiency of the reaction solvent rectifying tower T-52 and reduce the energy consumption.

In the invention, a discharge pump and an adjusting valve can be arranged between the outlet of the tower top of the alcohol rectifying tower T-51 and the alcohol heat exchanger E-51 for controlling the discharge and reflux ratio. The reaction solvent rectifying column T-52 can be provided with a discharge pump and an adjusting valve between the outlet of the top of the column and the solvent heat exchanger E-53 for controlling the discharge and reflux ratio.

In the invention, the various devices, such as the tank, the tower, the device, the kettle, the centrifuge and the like can be respectively provided with a feed inlet and/or a discharge outlet according to requirements, wherein the feed inlet is used for receiving introduced materials, and the discharge outlet is used for discharging the materials. One or more feed inlets and discharge outlets can be arranged according to actual needs.

In the invention, stirring mechanisms can be arranged in the reaction liquid mixing kettle R-11, the alkali dissolving kettle R-21, the ionomer reactor R-22, the washing kettle R-32 and the copolymerization reactor R-12. The stirring mechanism is used for stirring materials in the kettle or the reactor when needed, so that mass transfer is more sufficient. In addition, jackets can be arranged in the reaction liquid mixing kettle R-11, the alkali dissolving kettle R-21, the ionomer reactor R-22, the washing kettle R-32 and the copolymerization reactor R-12, and the temperature can be regulated and controlled by circulating water.

In the present invention, the system may further include:

and the metering pumps are arranged between the reaction liquid mixing kettle R-11 and the copolymerization reactor R-12, between the copolymerization reactor R-12 and the first disk centrifuge S-21, between the alkali liquor kettle V-21 and the ionomer reactor R-22, between the ionomer reactor R-22 and the second disk centrifuge S-22, between the alcohol storage tank V-37 and the washing kettle R-32, and between the washing kettle R-32 and the third disk centrifuge S-31.

In the present invention, the first disk centrifuge, the second disk centrifuge and the third disk centrifuge included in the above system are preferably selected to have a separation factor of more than 9000, preferably 9000-. The disc centrifuge within the limited range can better meet the requirement that the centrifugal separation of microsphere-containing materials is realized under the condition of high concentration by the system provided by the invention, the continuous operation of the system is realized, and the risk of sudden empty operation is reduced.

In the context of the present invention, the separation factor refers to the ratio of the centrifugal force to which the suspension or emulsion in the centrifuge is subjected in the centrifugal force field to its gravitational force, i.e. the ratio of the centrifugal acceleration to the gravitational acceleration. The separation factor is expressed as Fr: wherein R is the radius (meter) of the position of the separated material in the rotary drum; ω is the rotational angular velocity (radians/sec) of the drum; g is the acceleration of gravity (9.81 m/s)²) (ii) a n is the rotating drum rotating speed (revolution/minute); and m is the mass (kg) of the materials in the rotary drum. The separation factor is a primary measure of centrifuge performance. The larger Fr, the greater the driving force for centrifugal separationThe better the separation performance of the core machine

In a second aspect, the present invention provides a method for preparing crosslinked maleic acid ionomer microspheres using the system of the present invention, as shown in fig. 5, comprising:

(2) continuously carrying out first separation on the polymer mother liquor to obtain a separated solid-containing phase and a separation liquid;

r is H or methyl.

According to the present invention, the amount of each raw material used in step (1) is not particularly limited, and preferably, in step (1), the amount of monomer B is 50 to 150mol, more preferably 75 to 100mol, relative to 100mol of maleic anhydride. Wherein, the monomer B can be alpha-methyl styrene or styrene.

According to the invention, the initiator is preferably used in an amount of 0.05 to 10mol, more preferably 1 to 1.5mol, relative to 100mol of maleic anhydride.

According to the present invention, the crosslinking agent is preferably used in an amount of 1 to 40mol, more preferably 10 to 20mol, and further preferably 15 to 20mol, relative to 100mol of maleic anhydride.

According to the present invention, the reaction solvent is preferably used in an amount of 50 to 150L, more preferably 75 to 100L, relative to 100mol of maleic anhydride.

In the step (1) of the present invention, the conditions of the copolymerization reaction are not particularly limited, but preferably, the conditions of the copolymerization reaction are such that the degree of crosslinking of the copolymer microspheres obtained is 65% or more. More preferably, in step (1), the copolymerization reaction conditions include: under inert atmosphere, the temperature is 50-90 ℃, preferably 60-70 ℃, and the time is 3-15h, preferably 3-12 h. The inert atmosphere may be nitrogen or argon.

In the step (1) of the present invention, the reaction solvent may be any solvent commonly used in solution polymerization, for example, the reaction solvent includes organic acid alkyl ester, that is, organic acid alkyl ester, or a mixture of organic acid alkyl ester and alkane, or a mixture of organic acid alkyl ester and aromatic hydrocarbon. Wherein the organic acid alkyl esters include, but are not limited to: at least one of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate. Such alkanes include, but are not limited to: n-hexane and/or n-heptane. The aromatic hydrocarbons include, but are not limited to: at least one of benzene, toluene and xylene.

In step (1) of the present invention, the initiator may be a reagent commonly used in the art for initiating the polymerization reaction of maleic anhydride and α -methylstyrene (or styrene), and may be a thermal decomposition type initiator. Preferably, the initiator is at least one selected from the group consisting of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, and azobisisoheptonitrile.

In step (1) of the present invention, the crosslinking agent is divinylbenzene and/or an acrylate crosslinking agent containing at least two acrylate groups, and the acrylate groups have the structural formula: -O-C (O) -C (R') ═ CH₂R' is H or C₁-C₄Alkyl (e.g., methyl); preferably, the crosslinking agent is selected from divinylbenzene, 1, 3-propanediol dimethacrylate, 1, 2-propanediol dimethacrylate, 1, 3-propanediol diacrylate, 1, 2-propanediol diacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, phthalic acid diethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol, and/acrylate, polyethylene glycol, and/styrene, polyethylene glycol, and/acrylate, polyethylene glycol, and/acrylate, polyethylene glycol, and/styrene, at least one of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate.

According to the invention, in step (3), the base is used in an amount such that the molar amount of metal cations in the final ionomer obtained by said reaction is within a certain range compared to the percentage of structural units derived from maleic anhydride in the ionomer. Preferably, the base is used in an amount of 10 to 200mol with respect to 100mol of maleic anhydride. May be 10mol, 20mol, 50mol, 80mol, 100mol, 120mol, 150mol, 160mol, 180mol, 200mol or any value in between the above values.

In the present invention, the base may be a basic substance conventionally used in the art, or a basic substance capable of providing a metal cation. Preferably, the base may be selected from a hydroxide of the metal and/or an acetate of the metal. The metal may be a monovalent metal or a divalent metal, such as a group IA, IIA and/or IIB metal, preferably at least one of lithium, sodium, potassium, calcium, barium, zinc and magnesium. More preferably, the base is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, magnesium hydroxide, lithium acetate, sodium acetate, potassium acetate, calcium acetate, barium acetate, and zinc acetate.

According to the invention, the concentration of the lye may preferably be in the range of 1 to 50% by weight.

According to the invention, step (3) involves reacting said separated solid-containing phase with a base solution to obtain an ionomer. Preferably, the reaction temperature is 20-80 ℃, preferably 30-70 ℃, and the reaction time is 0.5-8h, preferably 0.5-3 h.

According to the invention, step (4) is used for washing the centrifuged slag phase to remove residues of the copolymerization and the reaction in step (3). Preferably, the alcohol wash uses a total of 100-250L of alcohol solvent, more preferably 150-200L, relative to 100mol of maleic anhydride. Preferably, the alcoholic solvent is selected from methanol or ethanol.

According to the invention, the separation of the microspheres from the resulting material containing microspheres is carried out in steps (2), (3) and (4). For example, the polymer mother liquor containing the maleic anhydride-based copolymer microspheres in the step (2) is subjected to first separation; performing second separation on the product containing the ionomer microspheres in the step (3); and (4) carrying out continuous third separation on the centrifugal slag phase containing the copolymer microspheres after the alcohol washing in the step (4). The materials containing the microspheres are subjected to solid-liquid separation under the condition of high concentration to obtain the high-purity and superfine microspheres. Preferably, the separation factor of the first separation in step (2) is greater than 9000, preferably 9000-; the separation factor of the second separation in step (3) is greater than 9000, preferably 9000-; the separation factor of the third separation in step (4) is greater than 9000, preferably 9000-. Within the above-mentioned range of separation factors, the above-mentioned separation in steps (2) to (4) of the present invention can be achieved under the condition of high concentration of microspheres content to realize industrial continuous operation.

In the step (5) of the present invention, the drying temperature is 50-150 ℃, and the drying pressure may be 10-1013mbar, preferably 10-200mbar, to further remove the reaction solvent and/or alcohol solvent entrained in the slag phase.

In the present invention, step (6) is used for recovering the solvent and the alcohol, and is performed in the solvent recovery unit of the system provided by the present invention. And the operation and control conditions of each part of devices in the solvent recovery unit meet the requirements of recovering the reaction solvent and the alcohol in the separation liquid-I, the separation liquid-II and the washing clear liquid. The operating conditions are not described in detail.

In the method provided by the invention, the aim of the invention can be better achieved under the limited conditions, the continuous preparation of the maleic acid ionomer with the cross-linking and microsphere structures is realized, the sudden empty operation of a solvent is avoided, and the frequent start-up and shutdown operations of a centrifuge are avoided.

The present invention will be described in detail below by way of examples.

In the following examples, the infrared spectroscopic analysis of the prepared maleic anhydride-based copolymer microspheres was carried out by a Spectrum Two instrument from PerkinElmer;

conditions of vacuum drying: the vacuum degree is-0.095 MPa at 100 ℃ and the time is 8 h.

The average particle size is determined by selecting 300-500 microspheres from a scanning electron microscope picture, measuring the diameter of the microspheres and calculating the average particle size of the microspheres by a mathematical average method;

scanning Electron microscopy analysis was determined by an XL-30ESEM-FEG instrument from FEI.

The method for measuring the degree of crosslinking comprises the following steps: weighing 2-3g of cross-linked maleate ionomer microsphere microspheres (w1), wrapping with medium-speed qualitative filter paper, placing into a Soxhlet extractor, extracting with tetrahydrofuran for 24h, drying and weighing the obtained residue (w2),

turbidity: the turbidity value is characterized by the concentration of particles (mass in g of particles in 100g of solvent, in% by weight) as determined using a turbidimeter.

Example 1

Isoamyl acetate is stored in a reaction solvent storage tank V-13; preparing a reaction solution in a reaction solution mixing kettle R-11: 1014mol of maleic anhydride, 12.2mol of azobisisobutyronitrile, 200mol of divinylbenzene, 1000mol of alpha-methyl styrene and 1000L of isoamyl acetate.

The reaction solution is put into a copolymerization reactor R-12 (two full mixing kettle type reactors connected in parallel), and copolymerization reaction is carried out for 5 hours at 75 ℃ in the atmosphere of nitrogen. Adding the polymerization mother liquor containing the maleic anhydride-based copolymer microspheres obtained by the reaction into a first disk centrifuge S-21 through a metering pump (the flow rate is 100kg/h) to perform continuous first separation (separation factor 9000), conveying the separated separation liquid I into a separation liquid storage tank V-25 when the turbidity is less than 0.1 wt% through a first online turbidity meter A-21, and returning the separation liquid I to a copolymerization reactor R-12 when the turbidity is more than 0.1 wt%. The separated solids-containing phase obtained by the centrifugal separation is fed to an ionomer reactor R-22.

Preparing 10 wt% sodium hydroxide aqueous solution in an alkali dissolving kettle R-21, adding the aqueous solution into an alkali liquor tank V-21 for standby, separating a solid-containing phase, feeding the separated solid-containing phase into an ionomer reactor R-22 (a full mixing kettle type reactor), simultaneously feeding alkali liquor in the alkali liquor tank V-31 into the ionomer reactor R-22 through a metering pump, reacting at 50 ℃ at the flow rate of 20kg/h (relative to 100mol of maleic anhydride, the amount of sodium hydroxide is 80mol), and keeping the reaction time for 1 h.

Continuously adding a product obtained by the reaction of the ionomer reactor R-22 into a second disc centrifuge S-22 from the bottom by a metering pump (the flow is 50kg/h) for second separation (separation factor 9000) to obtain a centrifugal slag phase containing ionomer microspheres, a water phase and a separation liquid-II; and conveying the separated liquid-II into a separated liquid storage tank V-25 for refining and recycling, conveying the water phase into an alkali dissolving kettle R-21 for recycling, and conveying the centrifugal slag into a washing kettle R-32 by difference. The effect of the second separation can be judged by controlling the turbidity by the second online turbidity meter A-22a and the third online turbidity meter A-22b, the water phase and the separating liquid-II are returned to the ionomer reactor R-22 when the turbidity is more than 0.1 wt%, the water phase is sent to the alkali dissolving kettle R-21 when the turbidity is less than 0.1 wt%, and the separating liquid-II is sent to the separating liquid storage tank V-25 when the turbidity is less than 0.1 wt%.

Feeding the methanol in the alcohol storage tank V-37 into a washing kettle R-32 by a metering pump, wherein the flow rate is 143kg/h, and carrying out alcohol washing on the centrifugal slag phase for 1 h; the alcohol washing product is sent into a third disk centrifuge S-31 by a metering pump (the flow is 173kg/h) for third separation (the separation factor is 9000), the obtained washing clear liquid is sent into a clear liquid storage tank V-36 when the turbidity is judged to be less than 0.1 weight percent by a fourth online turbidity meter A-31, and the washing clear liquid is returned into a washing kettle R-32 when the turbidity is more than 0.1 weight percent.

Conveying the ionomer slag phase into a rake vacuum dryer G-41(43kg/h) according to the material level, drying the slag phase in the rake vacuum dryer at the drying temperature of 140 ℃, the pressure of 80mbar, the retention time of 4h and the condensation temperature of a condenser E-41 of 0 ℃ to obtain the crosslinked maleic acid ionomer microspheres with the yield of 16.3 kg/h.

Carrying out infrared spectroscopic analysis on the microspheres, as shown in figure 1, displaying a sodium maleate characteristic peak and an aromatic ring characteristic peak, and proving the structure of the target ionomer; scanning electron microscope analysis is carried out on the microspheres, and as shown in figure 2, the microspheres are shown to have a microsphere structure; the average particle size was determined to be 1521 nm. The degree of crosslinking was determined to be 81%.

And the full mixing kettle type reactor R-12B and the full mixing kettle type reactor R-12A are connected in parallel and alternately discharged.

And respectively introducing the separated liquid in the separated liquid storage tank V-25 and the clear liquid in the clear liquid storage tank V-36 into a reaction solvent rectifying tower T-52 in the reaction solvent recovery device and an alcohol rectifying tower T-51 in the alcohol solvent recovery device, and respectively recovering the reaction solvent and the methanol for recycling. The methanol recovery and reaction solvent recovery conditions were as follows:

	alcohol rectifying tower T-51	Rectification of the reaction solventTower T-52
			Overhead temperature/. degree.C	68.9	74.0
Temperature of the bottom of the column/. degree.C	156.3	173.5
			Operating pressure/bar (gauge pressure)	1.4bar	-0.9bar
Reflux ratio	0.13	0.3

Example 2

Isoamyl acetate is stored in a reaction solvent storage tank V-13; preparing a reaction solution in a reaction solution mixing kettle R-11: 1014mol of maleic anhydride, 10.14mol of azobisisobutyronitrile, 150mol of divinylbenzene, 750mol of alpha-methyl styrene and 900L of isoamyl acetate.

The reaction liquid enters a tubular reactor R-12 with the feeding amount of 100kg/h, and the outlet temperature of the tubular reactor R-12 is controlled at 90 ℃ for 3h under the nitrogen atmosphere. Adding the polymerization mother liquor containing the maleic anhydride-based copolymer microspheres obtained by the reaction from an outlet (the flow rate is 100kg/h) of the reactor R-12 into a first disk centrifuge S-21 for continuous first separation (the separation factor is 12000), conveying the separated liquid into a separated liquid storage tank V-25 when the turbidity is less than 0.1 weight percent through a first online turbidity meter A-21, and returning the separated liquid to the copolymerization reactor R-12 when the turbidity is more than 0.1 weight percent. The separated solids-containing phase obtained by the centrifugal separation is fed to an ionomer reactor R-22.

Preparing 20 wt% potassium hydroxide aqueous solution in an alkali dissolving kettle R-21, adding the aqueous solution into an alkali liquor tank V-21 for standby, separating a solid-containing phase, feeding the separated solid-containing phase into an ionomer reactor R-22 (a tubular reactor), simultaneously feeding alkali liquor in the alkali liquor tank V-31 into the ionomer reactor R-22 by a metering pump, controlling the flow rate to be 16kg/h (relative to 100mol of maleic anhydride and the amount of potassium hydroxide to be 100mol), controlling the temperature of the reactor to be 50 ℃ and the retention time to be 1 h.

Continuously adding a product obtained by the reaction of the ionomer reactor R-22 into a second disc centrifuge S-22 from an outlet by a metering pump (the flow is 46kg/h) for second separation (the separation factor is 12000) to obtain a centrifugal slag phase containing ionomer microspheres, a water phase and a separation liquid-II; and conveying the separated liquid-II into a separated liquid storage tank V-25 for refining and recycling, conveying the water phase into an alkali dissolving kettle R-21 for recycling, and conveying the centrifugal slag into a washing kettle R-32 by difference. The effect of the second separation can be judged by controlling the turbidity by the second online turbidity meter A-22a and the third online turbidity meter A-22b, the water phase and the separating liquid-II are returned to the ionomer reactor R-22 when the turbidity is more than 0.1 wt%, the water phase is sent to the alkali dissolving kettle R-21 when the turbidity is less than 0.1 wt%, and the separating liquid-II is sent to the separating liquid storage tank V-25 when the turbidity is less than 0.1 wt%.

Feeding the washing methanol in the alcohol storage tank V-37 into a washing kettle R-32 through a metering pump, wherein the flow rate is 133kg/h, and carrying out alcohol washing on the centrifugal slag phase for 1 h; the alcohol washing product is sent into a second disk centrifuge S-31 by a metering pump (the flow is 167kg/h) for third separation (the separation factor is 12000), the obtained washing clear liquid is sent into a clear liquid storage tank V-36 when the turbidity is judged to be less than 0.1 weight percent by a fourth online turbidity meter A-31, and the washing clear liquid is returned into a washing kettle R-32 when the turbidity is more than 0.1 weight percent.

Conveying the ionomer slag phase into a rake vacuum dryer G-41(44kg/h) according to the material level, drying the slag phase in the rake vacuum dryer at the drying temperature of 50 ℃, the pressure of 10mbar, the retention time of 4h, the condensation temperature of a condenser E-41 of 0 ℃ and the yield of 16.5kg/h cross-linked maleic acid ionomer microspheres.

Carrying out infrared spectrum analysis on the microspheres, displaying a potassium maleate characteristic peak and an aromatic ring characteristic peak, and proving the structure of the target polymer; carrying out scanning electron microscope analysis on the microspheres to show that the microspheres have a microsphere structure; the average particle size was determined to be 1600 nm. The degree of crosslinking was determined to be 78%.

example 3

Isoamyl acetate is stored in a reaction solvent storage tank V-13; preparing a reaction solution in a reaction solution mixing kettle R-11: 1014mol of maleic anhydride, 15mol of azobisisobutyronitrile, 180mol of divinylbenzene, 850mol of alpha-methyl styrene and 850L of isoamyl acetate.

And (3) feeding the reaction liquid into a groove type baffling reactor R-12 with the feeding amount of 100kg/h, and controlling the outlet temperature of the groove type baffling reactor R-12 to be 85 ℃ and the retention time to be 3h under the nitrogen atmosphere.

Adding the polymerization mother liquor containing the maleic anhydride-based copolymer microspheres obtained by the reaction from an outlet (the flow rate is 100kg/h) of the reactor R-12 into a first disk centrifuge S-21 for continuous first separation (the separation factor is 14000), conveying the separated liquid into a separated liquid storage tank V-25 when the turbidity is less than 0.1 weight percent through a first online turbidity meter A-21, and returning the separated liquid to the copolymerization reactor R-12 when the turbidity is more than 0.1 weight percent. The separated solids-containing phase obtained by the centrifugal separation is fed to an ionomer reactor R-22.

Preparing 50 wt% sodium hydroxide aqueous solution in an alkali dissolving kettle R-21, adding the aqueous solution into an alkali liquor tank V-21 for standby, separating a solid-containing phase to enter an ionomer reactor R-22 (a groove type baffled reactor), simultaneously sending alkali liquor in the alkali liquor tank V-31 into the ionomer reactor R-22 by a metering pump, controlling the temperature of the reactor at 30 ℃ at a flow rate of 1.1kg/h (relative to 100mol of maleic anhydride and the amount of the hydrogen hydroxide is 20mol), and keeping the time at 0.5 h.

Continuously adding a product obtained by the reaction of the ionomer reactor R-22 into a second disc centrifuge S-22 from the bottom by a metering pump (the flow rate is 33kg/h) for second separation (the separation factor is 14000) to obtain a centrifugal slag phase containing ionomer microspheres, a water phase and a separation liquid-II; and conveying the separated liquid-II into a separated liquid storage tank V-25 for refining and recycling, conveying the water phase into an alkali dissolving kettle R-21 for recycling, and conveying the centrifugal slag into a washing kettle R-32 by difference. The effect of the second separation can be judged by controlling the turbidity by the second online turbidity meter A-22a and the third online turbidity meter A-22b, the water phase and the separating liquid-II are returned to the ionomer reactor R-22 when the turbidity is more than 0.1 wt%, the water phase is sent to the alkali dissolving kettle R-21 when the turbidity is less than 0.1 wt%, and the separating liquid-II is sent to the separating liquid storage tank V-25 when the turbidity is less than 0.1 wt%.

Feeding the washing methanol in the alcohol storage tank V-37 into a washing kettle R-32 by a metering pump, wherein the flow rate is 180kg/h, and carrying out alcohol washing on the centrifugal slag phase for 1 h; the alcohol washing product is sent into a third disk centrifuge S-31 by a metering pump (the flow is 213kg/h) for third separation (the separation factor is 14000), the obtained washing clear liquid is sent into a clear liquid storage tank V-36 when the turbidity is judged to be less than 0.1 weight percent by a fourth online turbidity meter A-31, and the washing clear liquid is returned into a washing kettle R-32 when the turbidity is more than 0.1 weight percent.

Conveying the ionomer slag phase into a rake vacuum dryer G-41(47kg/h) according to the material level, drying the slag phase in the rake vacuum dryer at the drying temperature of 90 ℃, the pressure of 100mbar, the retention time of 4h, the condenser condensation temperature of 0 ℃ and the yield of 17.8 kg/h.

Carrying out infrared spectroscopic analysis on the microspheres to display a sodium maleate characteristic peak and an aromatic ring characteristic peak, and proving the structure of the target polymer; carrying out scanning electron microscope analysis on the microspheres to show that the microspheres have a microsphere structure; the average particle size was determined to be 2000 nm. The degree of crosslinking was determined to be 80%.

	alcohol rectifying tower T-51	Reaction solvent rectifying tower T-52
			Overhead temperature/. degree.C	68.9	74.0
Temperature of the bottom of the column/. degree.C	156.3	173.5
			Operating pressure/bar (gauge pressure)	1.4bar	-0.9bar
Reflux ratio	0.13	0.3

Comparative example 1

The following reaction liquid is prepared in a polymer reaction kettle: 1014mol of maleic anhydride, 12.2mol of azobisisobutyronitrile, 200mol of divinylbenzene, 1000mol of alpha-methyl styrene and 1000L of isoamyl acetate.

Heating the reaction solution to 75 ℃ (the heating time is 1h), and carrying out copolymerization reaction for 5h at 75 ℃; and (3) carrying out solid-liquid separation on the polymerization mother liquor containing the maleic anhydride-based copolymer microspheres obtained by the reaction by using a three-leg centrifuge. In order to ensure safety, the reaction solution needs to be cooled to 30 ℃ (the cooling time is 1 h). The separation time was 2 h/batch (number of batches depends on whether the filter was clogged). After separation, the centrifuge was stopped for 1 h. Separating to obtain separated solid-containing phase.

The separated solid-containing phase was manually added to an ionomer reactor (material transfer, atmosphere replacement time 1h), 250kg of a 10 wt% aqueous solution of sodium hydroxide was added from an alkali solution tank, and the reaction was carried out at 50 ℃ for 1 h. And (3) carrying out solid-liquid separation on the maleic acid ionomer microsphere reaction liquid obtained by the reaction by using a three-leg centrifuge. In order to ensure safety, the temperature of the reaction solution is reduced to 30 ℃ (the temperature reduction time is 0.5 h). The separation time was 2 h/batch (number of batches depends on whether the filter was clogged). After separation, the centrifuge was stopped for 1 h. Separating to obtain centrifugal slag phase.

The centrifugal slag phase is manually added into a washing kettle (the time for material transfer and atmosphere replacement is 1 h). The washing methanol was transferred from the alcohol tank by means of a metering pump into the washing vessel and stirred for 1 h. The obtained washing liquid is added into a three-leg centrifuge by a metering pump for separation, the separation time is 2 h/batch (the batch number depends on whether the filter material is blocked), and after separation, the centrifuge is stopped for 1 h. A slag phase is obtained.

The slag phase is manually added into a rake vacuum drier G-41 (the time for material transfer and atmosphere replacement is 1h), the slag phase is dried in the rake vacuum drier at the drying temperature of 140 ℃ (the temperature rise time is 1h), the pressure is 80mbar, the retention time is 4h, the condenser condensation temperature is 0 ℃, and the yield is 203kg of the crosslinked alpha-methylstyrene/maleic acid ionomer microspheres.

The production efficiency of the batch operation was 7.7kg/h (solid-liquid separation of one batch was carried out using a three-leg centrifuge in each stage).

It can be seen from the results of the examples and the comparative examples that the continuous preparation of the maleic acid ionomer having the cross-linked and microsphere structures can be realized by using the examples 1 to 4 of the present invention, the separation process of manual operation between the units of the preparation system in the prior art is overcome, the obvious effects of higher production efficiency and stable production process are achieved, the production process does not need manual field operation, no organic solvent explosion operation exists, and the harm to personnel and environment is low.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A system for preparing crosslinked maleic acid ionomer microspheres, the system comprising:

the copolymerized units include: a reaction solvent storage tank (V-13), a reaction liquid mixing kettle (R-11), a copolymerization reactor (R-12), a first disk centrifuge (S-21), a first on-line turbidity meter (A-21) and a separation liquid storage tank (V-25);

the ionomer-generating reaction unit comprises: an alkali dissolving kettle (R-21), an alkali liquor tank (V-21), an ionomer reactor (R-22), a second disc centrifuge (S-22), a second online turbidimeter (A-22a) and a third online turbidimeter (A-22 b);

the washing unit includes: an alcohol tank (V-37), a clear liquid tank (V-36) and at least one set of washing devices, each set of washing devices comprising: a washing kettle (R-32), a third disc centrifuge (S-31) and a fourth online turbidimeter (A-31);

2. The system according to claim 1, wherein the reaction solvent storage tank (V-13) is for storing a reaction solvent;

the reaction liquid mixing kettle (R-11) is used for mixing the reaction solvent and a plurality of reaction raw materials into reaction liquid;

a copolymerization reactor (R-12) for continuously subjecting the reaction liquid to the copolymerization reaction;

the obtained polymer mother liquor continuously flows into a first disc centrifuge (S-21) to carry out continuous first separation, and the obtained separation liquid-I passes through a first online turbidity meter (A-21) and then is introduced into a copolymerization reactor (R-12) or a separation liquid storage tank (V-25).

3. The system according to claim 1, wherein valves are provided between the first on-line turbidimeter (a-21) and the copolymerization reactor (R-12), between the first on-line turbidimeter (a-21) and the separation liquid storage tank (V-25), respectively, for passing the separation liquid-I into the separation liquid storage tank (V-25) when the turbidity of the separation liquid-I is up to the standard and into the copolymerization reactor (R-12) when the turbidity of the separation liquid-I is not up to the standard.

4. The system according to claim 1 or 2, wherein the alkali dissolution tank (R-21) is for dissolving alkali in water as lye;

a lye tank (V-21) for storing the lye therefrom to provide the reaction;

an ionomer reactor (R-22) for said reacting said separated solid-containing phase with said lye;

and continuously flowing the obtained ionomer reaction solution into a second disc centrifuge (S-22) for continuous second separation, and introducing the obtained water phase into an ionomer reactor (R-22), a separation solution storage tank (V-25) or an alkali dissolving kettle (R-21) after passing through a second online turbidimeter (A-22a) and a separation solution-II through a third online turbidimeter (A-22 b).

5. The system according to claim 1 or 2, wherein valves are respectively arranged between the second on-line turbidimeter (a-22a) and the ionomer reactor (R-22), between the second on-line turbidimeter (a-22a) and the alkali dissolution tank (R-21), between the third on-line turbidimeter (a-22b) and the ionomer reactor (R-22), between the third on-line turbidimeter (a-22b) and the centrate tank (V-25) for passing the centrate-II into the centrate tank (V-25) when the turbidity of the centrate-II is up to the standard, and for passing the aqueous phase into the alkali dissolution tank (R-21) when the turbidity of the aqueous phase is up to the standard, and for passing the aqueous phase and the centrate-II into the ionomer reactor (R-22) when the turbidity of the aqueous phase is not up to the standard.

6. The system according to claim 1 or 2, wherein an alcohol reservoir (V-37) is used for storing an alcohol solvent;

the washing kettle (R-32) is used for continuously carrying out alcohol washing on the centrifugal slag phase and the alcohol solvent to obtain dispersed slurry;

and continuously feeding the dispersed slurry into a third disc centrifuge (S-31) for continuous third separation, and feeding the obtained washing clear liquid into a washing kettle (R-32) or a clear liquid storage tank (V-36) after passing through a fourth online turbidimeter (A-31).

7. The system according to claim 1 or 2, wherein valves are provided between the fourth on-line turbidimeter (a-31) and the wash tank (R-32), between the fourth on-line turbidimeter (a-31) and the clear liquid tank (V-36), respectively, for passing the wash clear liquid into the clear liquid tank (V-36) when the turbidity of the wash clear liquid is up to standard and for passing the wash clear liquid into the wash tank (R-32) when the turbidity is not up to standard.

8. The system of claim 1 or 2, wherein the drying unit comprises: a dryer (G-41), a condenser (E-41) and a dry condensate tank (V-41); wherein the content of the first and second substances,

the dryer (G-41) is used for drying the ionomer slag phase to obtain the crosslinked maleic acid ionomer microspheres;

the condenser (E-41) is communicated with the drying condensate tank (V-41) and is used for condensing the gaseous solvent discharged by the condensing dryer (G-41) into liquid and introducing the liquid into the drying condensate tank (V-41);

the drying gel tank (V-41) is communicated with an alcohol storage tank (V-37).

9. The system of claim 1 or 2, wherein the solvent recovery unit comprises: an alcohol solvent recovery device and a reaction solvent recovery device; wherein the content of the first and second substances,

the alcohol solvent recovery device is communicated with the clear liquid storage tank (V-36), the alcohol storage tank (V-37) and the reaction solvent recovery device, is used for recovering the alcohol solvent in the washing clear liquid from the clear liquid storage tank (V-36), returns to the alcohol storage tank (V-37), and simultaneously leads residual liquid of the washing clear liquid to the reaction solvent recovery device;

and the reaction solvent recovery device is communicated with the separation liquid storage tank (V-25) and the reaction solvent storage tank (V-13) and is used for recovering the separation liquid from the separation liquid storage tank (V-25) and the reaction solvent in the residual liquid and returning the separation liquid and the reaction solvent to the reaction solvent storage tank (V-13).

10. The system of claim 9, wherein the alcohol solvent recovery device comprises: an alcohol rectifying tower (T-51), an alcohol heat exchanger (E-51), an alcohol condensate tank (V-51) and a raffinate reboiler (E-52);

wherein the alcohol rectifying tower (T-51) is used for distilling the washing clear liquid from the clear liquid storage tank (V-36), and the alcohol vapor discharged from the top of the alcohol rectifying tower (T-51) passes through the alcohol heat exchanger (E-51) and the alcohol condensate tank (V-51) in turn to obtain the recovered alcohol; a part of the recovered alcohol is returned to an alcohol rectification column (T-51), and another part of the recovered alcohol is returned to an alcohol storage tank (V-37) to be reused in the washing unit;

and discharging a raffinate from the bottom of the alcohol rectification column (T-51), wherein a part of the raffinate is returned to the alcohol rectification column (T-51) after passing through a raffinate reboiler (E-52), and the other part of the raffinate is passed to the reaction solvent recovery unit.

11. The system of claim 9, wherein the reaction solvent recovery device comprises: a feeding tank (V-55), a reaction solvent rectifying tower (T-52), a solvent heat exchanger (E-53), a solvent condensate tank (V-53) and a waste liquid reboiler (E-54);

wherein the feed tank (V-55) communicates the bottom of the alcohol rectification column (T-51) and the separated liquid storage tank (V-25) for mixing the residue and the separated liquid from the separated liquid storage tank (V-25) as a feed;

the reaction solvent rectifying tower (T-52) is used for fractionating the feed, and the solvent vapor discharged from the top of the reaction solvent rectifying tower (T-52) passes through the solvent heat exchanger (E-53) and the solvent condensate tank (V-53) in sequence to obtain a recovered solvent; one part of the recovered solvent is returned to the reaction solvent rectifying tower (T-52), and the other part of the recovered solvent is returned to the reaction solvent storage tank (V-13) to be reused in the copolymerization unit;

and discharging waste liquid from the bottom of the reaction solvent rectifying tower (T-52), wherein one part of the waste liquid returns to the reaction solvent rectifying tower (T-52) after passing through a waste liquid reboiler (E-54), and the other part of the waste liquid is discharged.

12. A method of using the system of any one of claims 1-11 for making crosslinked maleic acid ionomer microspheres comprising:

r is H or methyl.

13. The process according to claim 12, wherein in the step (1), the monomer B is used in an amount of 50 to 150mol, the initiator is used in an amount of 0.05 to 10mol, the crosslinking agent is used in an amount of 1 to 40mol, and the reaction solvent is used in an amount of 50 to 150L, relative to 100mol of maleic anhydride.

14. The method of claim 12, wherein the copolymerization reaction conditions comprise: under inert atmosphere, the temperature is 50-90 ℃, and the time is 3-15 h.

15. The method of claim 12, wherein the separation factor of the first separation in step (2) is greater than 9000;

the separation factor of the second separation in step (3) is greater than 9000;

the separation factor of the third separation in step (4) is greater than 9000.

16. The method as claimed in claim 12, wherein the separation factor of the first separation in step (2) is 9000-;

the separation factor of the second separation in step (3) is 9000-;

the separation factor for the third separation in step (4) is 9000-.

17. The method as claimed in claim 12, wherein, in the step (4), a total of 100 and 250L of alcoholic solvent is used for the alcohol washing; the alcohol solvent is selected from methanol or ethanol.

18. The process according to claim 12, wherein, in the step (3), the amount of the base is 10 to 200mol with respect to 100mol of maleic anhydride; the concentration of the alkali liquor is 1-50 wt%; the reaction temperature is 20-80 ℃, and the reaction time is 0.5-8 h.